Solution equilibria and structural characterisation of the palladium(II) and mixed metal complexes of peptides containing methionyl residues.

Palladium(II) complexes of the peptides GlyMet, GlyMetGly and GlyGlyMet containing methionyl residues were studied by potentiometric and 1H NMR spectroscopic methods. The coordination of terminal amino and deprotonated amide nitrogen and thioether sulfur donor atoms was suggested in the mono complexes of GlyMet and GlyMetGly. The fourth coordination site of these complexes can be occupied by solvent molecule, chloride or hydroxide ions or by another ligand molecule in the bis or mixed ligand complexes. The second ligand coordinates monodentately via the thioether function in acidic media and the amino group under neutral or basic conditions. The stoichiometry of the major species formed in the palladium(II)-GlyGlyMet system is [PdH(-2) L]- and this is coordinated by the amino, two-amide and the thioether donor functions. Thioether bridged mixed metal complexes formed in the reaction of [Pd(dien)]2+ and [Cu(GlyMetH(-1))] or [Ni(GlyMetGlyH(-2))]- also have been detected by spectroscopic techniques.

The effect of histidyl residues on the complexation of bis(imidazolyl) containing tripeptides with copper(II) ion.

Copper(II) complexes of tripeptide derivatives of bis(imidazol-2-yl) group have been studied by potentiometric, UV-visible and EPR spectroscopic methods. The peptide molecules correspond to the amino acid sequence of collagen containing histidyl residues in different locations and were connected to the bis(imidazol-2-yl) group either on the C-termini (BOC-Pro-Leu-His-BIMA, BOC-His-Leu-Gly-BIMA) or on the N-termini (BIP-His-Ala-Gly-OEt, BIP-Ile-Ala-His-OMe). It was concluded that the imidazole nitrogen donor atoms of the bis(imidazol-2-yl) moiety are the primary metal binding sites, but the histidyl imidazole nitrogens in the side chains have also some effect on the stability and the coordination mode of the complexes. All ligands can coordinate tridentately to copper(II) ion forming a six-membered chelate and a macrochelate in the [CuL]2+ complexes, which results in a slight distortion in the coordination geometry of [CuL2]2+ complexes. The deprotonation and coordination of amide nitrogens, however, were not observed in any cases.

Potentiometric and spectroscopic studies on the copper(II) complexes of peptide hormones containing disulfide bridges.

Copper(II) complexes of oxytocin, 4-Glu-oxytocin, 5-Asp-oxytocin, and GlyGlyGly-Lys8-vasopressin were studied by potentiometric, EPR, and UV-visible spectroscopic methods. The formation of 4N-coordinated complexes was characteristic of all ligands. This type of coordination is especially favored for oxytocin due to the specific conformation of the ring coupled by the disulfide bridge. The coordination of the gamma-carboxylate group of 4-Glu-oxytocin and a disulfide sulfur atom of GlyGlyGly-Lys8-vasopressin was reported to occur in the 2N-complexes over medium pH range.

Metal binding ability of hypermodified nucleosides of t-RNA. Potentiometric and spectroscopic studies on the metal complexes of N-[(9-beta-D-ribofuranosylpurin-6-yl)-carbamoyl] threonine.

Copper(II), nickel(II), zinc(II), manganese(II), and magnesium(II) complexes of t6A (N-[9-beta-D-ribofuranosylpurin-6-yl)carbamoyl] threonine and t6Ade (N6(threoninocarbonyl)adenine) were studied by potentiometric and spectroscopic methods. It was found that t6Ade has three dissociable protons in the accessible pH range (N1 and N9 of purine and carboxylate), while only two pK values are characteristic of t6A. Magnesium(II) and manganese(II) do not interact effectively with these ligands, but copper(II) and nickel(II) ions form very stable complexes with the coordination of purine N1, deprotonated amide nitrogen, and carboxylate oxygen donors.

Transition metal complexes of L-cysteine containing di- and tripeptides.

Nickel(II), cobalt(II), zinc(II), and cadmium(II) complexes of Ala-Cys, Phe-Cys, and Ala-Ala-Cys were studied by potentiometric and spectroscopic methods. Ni(II) induces deprotonation and coordination of the amide nitrogens, and the stable monomeric or oligomeric complexes are formed, depending on the metal to ligand molar ratios. Formation of the stable bis-complexes with [S,O] coordination mode is characteristic for cobalt(II), zinc(II), and cadmium(II) ions.